Assembly of self-standing pouches

ABSTRACT

The present invention provides a shipping unit comprising more than one flexible pouch (15) and a secondary package (20). Each flexible pouch is filled with a granular laundry detergent. The secondary package contains the filled pouches of the shipping unit and keeps the filled pouches together in the shipping unit. The secondary package is in a closed position such to prevent the exit of any of the filled pouches prior to opening of the shipping unit. The secondary package is flexible and non-resistant to compression force when the shipping unit is stacked with other shipping units in an assembly, and the granular laundry detergent contained in each flexible pouch has a cake strength of less than or equal to 200 g/cm 2 . This shipping unit is able to carry the load of other stacked shipping units to form an assembly in form of a pallet.

FIELD OF THE INVENTION

The present invention relates to an assembly of self-standing flexiblepouches whereby the pouches contain granular or powdered products.

BACKGROUND OF THE INVENTION

A great variety of packages have been described which are suitable forpackaging granular or liquid detergent. A constant preoccupation ofdetergent manufacturers is to provide packaged goods which areconvenient to handle and in particular to store. This requirementincludes the possibility to stack packages so that minimum ground spaceis required.

Granular laundry detergents are known to be packed into flexiblepouches. The flexible pouches are such that they are not able to carryany load in an assembly when single or grouped flexible pouches arestacked one over another in the assembly during storing andtransportation of the flexible pouches. The load of the stacked assemblyis immediately transferred to the contained detergent. It has now beenfound that certain type of packaged granular or powdered detergents arenot able to carry the load and sustain the weight of other packagedgranular or powdered detergent when the packaged detegents are stackedin an assembly. Indeed, it is known that certain types of granulardetergent "cakes". To "cake" means in the following that the granular orpowdered detergent sticks or aggregates together forming lumps when putunder a compression force, like a top load. The caking may be such thatthe detergent aggregates into one insoluble block. The "caking" of adetergent may adversely affect the washing properties of the detergentitself.

The so called "cake strength" is a measure of the caking of a granularor powdered detergent. The "cake strength" is defined to be the forceneeded to disaggregate a caked detergent. This means that a lower cakestrength results in less caking of the detergent. For example, a cakestrength of 0 g/cm² means that the detergent does not cake. The cakestrength of a granular or powdered detergent varies with the compositionor manufacturing method of the detergent itself. Therefore, especiallywhen the pouches are filled with granular or powdered detergentsusceptible to caking, it is important to take care that the weight orload from the stacked assembly is not carried by the detergent.

To avoid caking of the granular or powdered detergent, the filledflexible pouches are usually combined into a shipping unit which isformed by a high strength outer case. This outer case is able to supportthe stacking of several shipping units in an assembly. This also meansthat only the outer case and not the filled pouches combined into theseouter cases carry the weight or support the compression force from thestacked assembly. This is certainly one way to avoid caking of thegranular or powdered detergent. However, the manufacturing cost of sucha packaging assembly is relatively high. Furthermore, the use of theabove mentioned outer cases increases the waste packaging materials.Indeed, the outer cases are usually not reusable after the storing andtransportation of the flexible pouches. Therefore, the manufacturers ofdetergent compositions are in need to reduce the costs of the packagingand to reduce the waste packaging materials necessary for handling,storing and transportation of detergent filled in flexible pouches.

It is therefore an object of the present invention to provide a shippingunit of flexible pouches, the flexible pouches being filled withgranular or powdered detergent less susceptible to caking when stackingother flexible pouches one over another, and without the need to combinethese filled, flexible pouches into outer cases which carry thecompression force from the stacked assembly.

SUMMARY OF THE INVENTION

The present invention is a shipping unit comprising more than oneflexible pouch and a secondary package. Each flexible pouch is filledwith a granular laundry detergent. The secondary package contains thefilled pouches of the shipping unit and keeps the filled pouchestogether in the shipping unit. The secondary package is closed so thatit prevents the exit of any of the filled pouches prior to opening ofthe shipping unit. The secondary package is flexible and non-resistantto compression force when the shipping unit is stacked with othershipping units in an assembly, and the granular laundry detergentcontained in each flexible pouch has a cake strength of less than orequal to 200 g/cm².

The present invention further provides an assembly of shipping unitsforming a pallet unit.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of part of the packaging machine showingthe method to assemble filled packages together into a secondary packageaccording to the present invention.

FIG. 2 illustrates the method to measure the cake strength of a granularor powdered detergent.

DETAILED DESCRIPTION OF THE INVENTION

As hereinafter understood, a pouch or a secondary package being"flexible and non-resistant to compression force" means that the pouchor the secondary package is such that it is not able to carry any loadin an assembly when single pouches or pouches grouped in a secondarypackage are stacked one over another in the assembly during storing andtransportation of the pouches. The load of the stacked assembly isimmediately transferred to the content of the pouches.

The pouch according to the present invention is flexible andnon-resistant to compression force. The flexible pouch is preferablymade of a material selected from the group consisting of: tissue, metalfoil, paper, plastic materials and a combination thereof. As plasticmaterials polyolefines, like polyethylene (=PE), or (oriented)polyethylene terephthalate, or (oriented) polypropylene or a combinationthereof, may be used. When the flexible pouch is made of a multi-layermaterial, the intermediate layers may comprise a perfume barrier layer,a gas barrier layer, an oxygen barrier layer, a moisture barrier layer,or a combination thereof. Preferably, the intermediate layer is made ofa material selected from the following group consisting of: aluminiumfoil, ethyl vinyl alcohol co-polymer (=EVOH), lacquer coating and acombination thereof. Possible lacquer coatings are, for example,Flexplastol® 2KB-Lacquer 9A 918 920 or Flexoplastol® 2KB-Lacquer 9A 919920 commercially available from BASF Lacke+Farben AG, Stuttgart.

The flexible pouch comprising multi-layers may be achieved by laminatingor extruding the layers together. The lamination of layers means thatthe different layers are attached to each other in a solid state, i.e.the different layer are not melted together as in the extrusion process.In the lamination process lower temperatures are used with respect tothe extrusion. As a preferred option, a tie layer may be used at leaston one side of the intermediate layers to strengthen the bonding betweenthe intermediate layers and the other layers. Said tie layer ispreferably made of glue. A preferred glue is a polyurethane-basedadhesive. By polyurethane-based adhesives it is intended all theadhesives based on polyurethane known to the person skilled in the art.In particular, solvent based (including water) and solvent-free adhesivesystems comprising polyurethane are usable for the purpose of thepresent invention. This tie layer can be also applied on both sides ofsaid intermediate layer and/or of the other layers.

Preferably, the flexible pouch according to the present invention is astand-up or self-standing pouch. This flexible, stand-up pouch may beformed in different possible ways. One possibility is a gusseted pouch.This type of pouches is described, for example, in EP-A-620 156, DE-A-2520 084, DE-A-3 926 728 and U.S. Pat. No. 3,659,775 which are herewithincorporated for further reference. These documents further describe theforming and filling process of these pouches. Another possibility is apouch having a broadened bottom base as described for example in EP-A-0626 319 and/or EP-A-0 681 970 which are also herewith incorporated forfurther reference. The same documents describe also the correspondingforming and filling process of these pouches.

Preferably, the stand-up pouch according to the present invention has anair-free portion. This means that the pouches are not completely filledwith the granular or powdered detergent and the remaining part of thevolume of the pouch is under a partial or substantially complete vacuum.This vacuum is maintained starting from an unfilled, flat pouch duringthe filling and sealing operation. The air-free portion is preferablyfolded to create a nearly flat surface. This nearly flat surface issufficiently great to support the base of another stacked pouch. Theair-free portion folded to a nearly flat surface is preferably fastenedwith adequate means. This fastening means may be, for example, selectedfrom the group consisting of: ligatures, adhesive tapes, straps, plasticfilm bands, shrinkable plastic film bands and any combination thereof.These fastening means are placed partially or completely around thepouch maintaining the air-free portion in a folded, nearly flat surface,therefore preventing this nearly flat surface to unfold. The folding ofthe air-free free portion and the fastening means are further describedand illustrated in EP-A-0 681 970 which is herewith incorporated forfurther reference.

The stand-up, flexible pouches according to the present invention arefilled with granular or powdered detergent having a cake strength ofless than or equal to 200 9/cm². Specifically, the cake strength ofgranular or powdered detergent having a density of up to 600 g/l is nomore than 200 g/cm². The cake strength of granular or powdered detergenthaving a density of greater than 600 g/l is preferably up to 100 g/cm²,more preferably less than 90 g/cm², even more preferably less than 80g/cm², even more preferably less than 60 g/cm², most preferably lessthan 50 g/cm². As said before, the cake strength is the strength neededto disaggregate a caked detergent. The cake strength of a granular or apowdered detergent is measured and determined in the following manner.

The apparatus for measuring the cake strength is shown in FIG. 2 andcomprises a cylinder (110), a sleeve (111), a lid (112), a locking pin(114), a weight (115) and a force gauge (not shown). The cylinderfurther comprises a hole (118) in which the locking pin can be inserted.The cylinder stands on its closed base (119), whereby the cylinder isfilled with detergent through the opposed open top end (120). Firstly,the locking pin (114) is inserted into the hole (118) and then thesleeve (111) is slid over the outermost surface of the cylinder untilthe sleeve rests on the locking pin. Thereby, the top end (121) of thesleeve remains higher than the top end (120) of the cylinder. The openvolume between the top end of the cylinder and the top end of the sleevehas following dimensions: diameter 6.35 cm and height 3 cm. This volumeis filled with a detergent up to the top end of the sleeve and levelledoff with the top end of the sleeve.

The lid (112) is now placed on top of the sleeve (111). Preferably, thelid is made of a very light material, but resistant enough to carry aload and able to compress the detergent. A preferred material isPerspex® (from ICI). The weight (115) is now placed on top of the lid.The total weight of the lid (112) together with the weight (115) is 5kg. The lid is further fastened to the sleeve to avoid that the lidmoves. The fastening of the lid to sleeve is achieved according to thepresent method stretching an elastic band around appropriate lugs (122)on the lid and the cylinder. Once the weight is placed on top of thelid, the locking pin (114) is removed from the hole (118). In thismanner, the weight compresses together the detergent located between thelid (112) and the top end (120) of the cylinder. The weight is leftaccording to the measurement standard of the present invention for twominutes. Thereafter, the weight is removed from the top of the lid. Allthe elastic bands are also removed.

The sleeve (111) is now gently slid down towards the closed end (119).Consequently, the detergent located between the lid (112) and the topend (120) of the cylinder is not confined anymore by any lateral walls.In principle, this detergent is free to flow away from this region.However, the free flow of the detergent located in this region dependsfrom the caking of this detergent experienced during the compression ofthe weight (115). Indeed, a partial caking of the detergent in thisregion may impede a free flow of the detergent. It has been found thatby applying a force on the detergent located in this region, thepossibly caked detergent disaggregates such that the detergent may befree to flow away again. The force needed to observe this free flow ofthe detergent from this region is the cake strength according to thepresent method of measurement. The cake strength is measured by a forcegauge which is applied onto the centre of the lid (112). Pressingincreasingly the force gauge onto the lid, an increasing amount of forceis applied onto the detergent. The force at which the detergentcollapses and freely flows away from the region between the lid and theopen end of the cylinder is considered to be the cake strength of thedetergent. These measurements of the cake strength are made at about 20°C. and within about 45% and 70% of relative humidity.

The Detergent Composition

By the term detergent composition herein is meant laundry detergentcompositions, as well as automatic dishwashing compositions and laundryadditive compositions.

The present compositions are characterized by their cake strength ofless than 100 g/cm².

Anionic Surfactants

In the preferred embodiment herein, where the detergent compositionsherein is a laundry detergent composition, compositions of the presentinvention usually contain one or more anionic surfactants as describedbelow.

Alkyl Sulfate Surfactant

Alkyl sulfate surfactants hereof are water soluble salts or acids of theformula ROSO₃ M wherein R preferably is a C₁₀ -C₂₄ hydrocarbyl,preferably an alkyl or hydroxyalkyl having a C₁₀ -₂₀ alkyl component,more preferably a C₁₂ -C₁₈ alkyl or hydroxyalkyl, and M is H or acation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium),or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, andtrimethyl ammonium cations and quaternary ammonium cations, such astetramethyl-ammonium and dimethyl piperdinium cations and quarternaryammonium cations derived from alkylamines such as ethylamine,diethylamine, triethylamine, and mixtures thereof, and the like).Typically, alkyl chains of C₁₂₋₁₆ are preferred for lower washtemperatures (e.g., below about 50° C.) and C₁₆₋₁₈ alkyl chains arepreferred for higher wash temperatures (e.g., above about 50° C.).

Alkyl Alkoxylated Sulfate Surfactant

Alkyl alkoxylated sulfate surfactants hereof are water soluble salts oracids of the formula RO(A)_(m) SO₃ M wherein R is an unsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀ -C₂₄ alkyl component,preferably a C₁₂ -₂₀ alkyl or hydroxyalkyl, more preferably C₁₂ -C₁₈alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater thanzero, typically between about 0.5 and about 6, more preferably betweenabout 0.5 and about 5, and M is H or a cation which can be, for example,a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.Specific examples of substituted ammonium cations include methyl-,dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such astetramethyl-ammonium, dimethyl piperdinium and cations derived fromalkanolamines such as ethylamine, diethylamine, triethylamine, mixturesthereof, and the like. Exemplary surfactants are C₁₂ -C₁₈ alkylpolyethoxylate (1.0) sulfate, C₁₂ -C₁₈ E(1.0)M), C₁₂ -C₁₈ alkylpolyethoxylate (2.25) sulfate, C₁₂ -C₁₈ E(2.25)M), C₁₂ -C₁₈ alkylpolyethoxylate (3.0) sulfate C₁₂ -C₁₈ E(3.0), and C₁₂ -C₁₈ alkylpolyethoxylate (4.0) sulfate C₁₂ -C₁₈ E(4.0)M), wherein M isconveniently selected from sodium and potassium.

Other Anionic Surfactants

Other anionic surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present inventionwith or without the species described above. These can include salts(including, for example, sodium, potassium, ammonium, and substitutedammonium salts such as mono-, di- and triethanolamine salts) of soap, C₉-C₂₀ linear alkylbenzenesulphonates, C₈ -C₂₂ primary or secondaryalkanesulphonates, C₈ -C₂₄ olefinsulphonates, sulphonated polycarboxylicacids prepared by sulphonation of the pyrolyzed product of alkalineearth metal citrates, e.g., as described in British patent specificationNo. 1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ehtylene oxide); alkyl ester sulfonates such as C₁₄₋₁₆ methylester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, paraffinsulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinate (especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters of sulfosuccinate (especially saturated andunsaturated C₆ -C₄ diesters), acyl sarcosinates, sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), branched primaryalkyl sulfates, alkyl polyethoxy carboxylates such as those of theformula RO(CH₂ CH₂ O)_(k) CH₂ COO--M⁺ wherein R is a C₈ -C₂₂ alkyl, k isan integer from 0 to 10, and M is a soluble salt-forming cation. Resinacids and hydrogenated resin acids are also suitable, such as rosin,hydrogenated rosin, and resin acids and hydrogenated resin acids presentin or derived from tall oil. Further examples are given in "SurfaceActive Agents and Detergents" (Vol. I and II by Schwartz, Perry andBerch). A variety of such surfactants are also generally disclosed inU.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. atColumn 23, line 58 through Column 29, line 23 (herein incorporated byreference).

Preferred surfactants for use in the compositions herein are the alkylsulfates, alkyl alkoxylated sulfates, and mixtures thereof.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 1% to about 40%, preferably fromabout 3% to about 20% by weight of such anionic surfactants.

Nonionic Surfactants

The present laundry detergent compositions preferably also comprise anonionic surfactant.

While any nonionic surfactant may be normally employed in the presentinvention, two families of nonionics have been found to be particularlyuseful. These are nonionic surfactants based on alkoxylated (especiallyethoxylated) alcohols, and those nonionic surfactants based on amidationproducts of fatty acid esters and N-alkyl polyhydroxy amine. Theamidation products of the esters and the amines are generally referredto herein as polyhydroxy fatty acid amides. Particularly useful in thepresent invention are mixtures comprising two or more nonionicsurfactants wherein at least one nonionic surfactant is selected fromeach of the groups of alkoxylated alcohols and the polyhydroxy fattyacid amides.

Suitable nonionic surfactants include compounds produced by thecondensation of aikylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromaticin nature. The length of the polyoxyalkylene group which is condensedwith any particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements.

Particularly preferred for use in the present invention are nonionicsurfactants such as the polyethylene oxide condensates of alkyl phenols,e.g., the condensation products of alkyl phenols having an alkyl groupcontaining from about 6 to 16 carbon atoms, in either a straight chainor branched chain configuration, with from about 4 to 25 moles ofethylene oxide per mole of alkyl phenol.

Preferred nonionics are the water-soluble condensation products ofaliphatic alcohols containing from 8 to 22 carbon atoms, in eitherstraight chain or branched configuration, with an average of up to 25moles of ethylene oxide per more of alcohol. Particularly preferred arethe condensation products of alcohols having an alkyl group containingfrom about 9 to 15 carbon atoms with from about 2 to 10 moles ofethylene oxide per mole of alcohol; and condensation products ofpropylene glycol with ethylene oxide. Most preferred are condensationproducts of alcohols having an alkyl group containing from about 12 to15 carbon atoms with an average of about 3 to 7 moles of ethylene oxideper mole of alcohol, preferably 3 to 5.

The nonionic surfactant system herein can also include a polyhydroxyfatty acid amide component.

Polyhydroxy fatty acid amides may be produced by reacting a fatty acidester and an N-alkyl polyhydroxy amine. The preferred amine for use inthe present invention is N-(R1)-CH2(CH2OH)4-CH2-OH and the preferredester is a C12-C20 fatty acid methyl ester. Most preferred is thereaction product of N-methyl glucamine with C12-C20 fatty acid methylester.

Methods of manufacturing polyhydroxy fatty acid amides have beendescribed in WO 92 6073, published on Apr. 16, 1992. This applicationdescribes the preparation of polyhydroxy fatty acid amides in thepresence of solvents. In a highly preferred embodiment of the inventionN-methyl glucamine is reacted with a C12-C20 methyl ester. It also saysthat the formulator of granular detergent compositions may find itconvenient to run the amidation reaction in the presence of solventswhich comprise alkoxylated, especially ethoxylated (EO 3-8) C12-C14alcohols (page 15, lines 22-27). This directly yields nonionicsurfactant systems which are preferred in the present invention, such asthose comprising N-methyl glucamide and C12-C14 alcohols with an averageof 3 ethoxylate groups per molecule.

Nonionic surfactant systems, and granular detergents made from suchsystems have been described in WO 92 6160, published on Apr. 16, 1992.This application describes (example 15) a granular detergent compositionprepared by fine dispersion mixing in an Eirich RV02 mixer whichcomprises N-methyl glucamide (10%), nonionic surfactant (10%).

Both of these patent applications describe nonionic surfactant systemstogether with suitable manufacturing processes for their synthesis,which have been found to be suitable for use in the present invention.

The polyhydroxy fatty acid amide may be present in compositions of thepresent invention at a level of from 0% to 50% by weight of thedetergent component or composition, preferably from 5% to 40% by weight,even more preferably from 10% to 30% by weight.

Also useful as the nonionic surfactant of the surfactant systems of thepresent invention are the alkylpolysaccharides disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from about 6 to about 30 carbon atoms, preferably from about10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside,hydrophilic group containing from about 1.3 to about 10, preferably fromabout 1.3 to about 3, most preferably from about 1.3 to about 2.7saccharide units. Any reducing saccharide containing 5 or 6 carbon atomscan be used, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties (optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside). The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3-, 4-, and/or 6- positions on thepreceding saccharide units.

The preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O).sub.t (glycosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably from about 1.3 to about 3, most preferably fromabout 1.3 to about 2.7. The glycosyl is preferably derived from glucose.To prepare these compounds, the alcohol or alkylpolyethoxy alcohol isformed first and then reacted with glucose, or a source of glucose, toform the glucoside (attachment at the 1-position). The additionalglycosyl units can then be attached between their 1-position and thepreceding glycosyl units 2-, 3-, 4- and/or 6-position, preferablypredominantly the 2-position.

Other Surfactants

The laundry detergent compositions of the present invention may alsocontain cationic, ampholytic, zwitterionic, and semi-polar surfactants,as well as nonionic surfactants other than those already describedherein, including the semi-polar nonionic amine oxides described below.

Cationic detersive surfactants suitable for use in the laundry detergentcompositions of the present invention are those having one long-chainhydrocarbyl group. Examples of such cationic surfactants include theammonium surfactants such as alkyldi- or tri-methylammonium compounds,and those surfactants having the formula:

    [R.sup.2 (OR.sup.3)y][R.sup.4 (OR.sup.3)y].sub.2 R.sup.5 N+X-

wherein R2 is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain, each R³ is selected from thegroup consisting of --CH₂ CH₂ --, --CH₂ CH(CH₃)--, --CH₂ CH(CH₂ OH)--,--CH₂ CH₂ CH₂ --, and mixtures thereof; each R⁴ is selected from thegroup consisting of C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, benzyl ringstructures formed by joining the two R⁴ groups, --CH₂ COH--CHOHCOR⁶CHOHCH₂ OH wherein R6 is any hexose or hexose polymer having a molecularweight less than about 1000, and hydrogen when y is not 0; R⁵ is thesame as R⁴ or is an alkyl chain wherein the total number of carbon atomsof R² plus R⁵ is not more than about 18; each y is from 0 to about 10and the sum of the y values is from 0 to about 15; and X is anycompatible anion.

Other cationic surfactants useful herein are also described in U.S. Pat.No. 4,228,044, Cambre, issued Oct. 14, 1980, incorporated herein byreference.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from 0% to about 25%, preferably form about3% to about 15% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the laundrydetergent compositions of the present invention. These surfactants canbe broadly described as aliphatic derivatives of secondary or tertiaryamines, or aliphatic derivatives of heterocyclic secondary and tertiaryamines in which the aliphatic radical can be straight- or branchedchain. One of the aliphatic substituents contains at least 8 carbonatoms, typically from about 8 to about 18 carbon atoms, and at least onecontains an anionic water-solubilizing group e.g. carboxy, sulfonate,sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30,1975 at column 19, lines 18-35 (herein incorporated by reference) forexamples of ampholytic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise form 0% to about 15%, preferably from about1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergentcompositions. These surfactants can be broadly described as derivativesof secondary and tertiary amines, derivates of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quarternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at columns 19, line 38 throughcolumn 22, line 48 (herein incorporated by reference) for examples ofzwitterionic surfactants.

When included therein, the laundry detergent compositions of the presentinvention typically comprise form 0% to about 15%, preferably from about1% to about 10% by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionicsurfactants which include water-soluble amine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting af alkyl groups and hydrocyalkylgroups containing form about 1 to about 3 carbon atoms; water-solublephosphine oxides containing one alkyl moiety of form about 10 to about18 carbon atoms and 2 moieties selected form the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to about 3carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula: ##STR1## Builder

The laundry detergent compositions and automatic dishwashingcompositions herein contain a builder, preferably non-phosphatedetergent builders, although phosphate-containing species are notexcluded in the content of the present invention. These can include, butare not restricted to alkali metal carbonates, bicarbonates, silicates,aluminosilicates, carboxylates and mixtures of any of the foregoing. Thebuilder system is present in an amount of from 1% to 80% by weight ofthe composition, typically preferable from 20% to 60% by weight ingranular laundry detergent compositions herein, and from 1% to 30% inliquid laundry detergent compositions herein.

Suitable silicates are those having an SiO₂ :Na₂ O ratio in the rangefrom 1.6 to 3.4, the so-called amorphous silicates of SiO₂ :Na₂ O ratiosfrom 2.0 to 2.8 being preferred.

Within the silicate class, highly preferred materials are crystallinelayered sodium silicates of general formula

    NaMSi.sub.x O.sub.2x +1.yH2O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is anumber from 0 to 20. Crystalline layered sodium silicates of this typeare disclosed in EP-A-0164514 and methods for their preparation aredisclosed in DE-A-3417649 and DE-A-3742043. For the purposes of thepresent invention, x in the general formula above has a value of 2,3 or4 and is preferably 2. More preferably M is sodium and y is 0 and apreferred example of this formula comprise the form of Na₂ Si₂ O₅. Thesematerials are available from Hoechst AG FRG as respectively NaSKS-5,NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is Na₂ Si₂O₅, NaSKS-6. Crystalline layered silicates are incorporated either asdry mixed solids, or as solid components of agglomerates with othercomponents.

Whilst a range of aluminosilicate ion exchange materials can be used,preferred sodium aluminosilicate zeolites have the unit cell formula

    Na.sub.z [(AIO.sub.2).sub.z.(SiO.sub.2).sub.y ].xH.sub.2 O

wherein z and y are at least about 6, the molar ratio of z to y is fromabout 1.0 to about 0.4 and z is from about 10 to about 264. Amorphoushydrated aluminosilicate materials useful herein have the empiricalformula

    M.sub.z (zAIO.sub.2.ySiO.sub.2)

wherein M is sodium, potassium, ammonium or substituted ammonium, z isfrom about 0.5 to about 2 and y is 1, said material having a magnesiumion exchange capacity of at least about 50 milligram equivalents ofCaCO₃ hardness per gram of anhydrous aluminosilicate. Hydrated sodiumZeolite A with a particle size of from about 0.01 to 10 microns ispreferred.

The aluminosilicate ion exchange builder materials herein are inhydrated form and contain from about 10% to about 28% of water by weightif crystalline, and potentially even higher amounts of water ifamorphous. Highly preferred crystalline aluminosilicate ion exchangematerials contain from about 18% to about 22% water in their crystalmatrix. The crystalline aluminosilicate ion exchange materials arefurther characterized by a particle size diameter of from about 0.1micron to about 10 microns. Amorphous materials are often smaller, e.g.,down to less than about 0.01 micron. Preferred ion exchange materialshave a particle size diameter of from about 0.2 micron to about 4microns. The term "particle size diameter" herein represents the averageparticle size diameter by weight of a given ion exchange material asdetermined by conventional analytical techniques such as, for example,microscopic determination utilizing a scanning electron microscope.

Aluminosilicate ion exchange materials useful in the practice of thisinvention are commercially available. The aluminosilicates useful inthis invention can be crystalline or amorphous in structure and can benaturally occurring aluminosilicates or synthetically derived. A methodfor producing aluminosilicate ion exchange materials is discussed inU.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976,incorporated herein by reference. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite X, P and MAP, the latter speciesbeing described in EPA 384 070. In an especially preferred embodiment,the crystalline aluminosilicate ion exchange material is a Zeolite Ahaving the formula

    Na.sub.12 [(AIO.sub.2).sub.12 (SiO2).sub.12 ].xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27 and has aparticle size generally less than about 5 microns.

Suitable carboxylate builders containing one carboxy group includelactic acid, glycollic acid and ether derivatives thereof as disclosedin Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylatescontaining two carboxy groups include the water-soluble salts ofsuccinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,diglycollic acid, tartaric acid, tartronic acid and fumaric acid, aswell as the ether carboxylates described in German Offenlegungschrift2,446,686 and 2,446,687 and U.S. Pat. No. 3,935,257 and the sulfinylcarboxylates described in Belgian Patent No. 840,623. Polycarboxylatescontaining three carboxy groups include, in particular, water-solublecitrates, aconitrates and citraconates as well as succinate derivativessuch as the carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in Netherlands Application7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829,1, and the 1,2,2-ethanetetracarboxylates ,1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,082,179,while polycarboxylates containing phosphone substituents are disclosedin British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates,2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates,2,5-tetrahydrofuran -cis-dicarboxylates,2,2,5,5,-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexanehexacarboxylates and carbxoymethyl derivatives of polyhydric alcoholssuch as sorbitol, mannitol and xyiitol. Aromatic polycarboxylatesinclude mellitic acid, pyromellitic acid and the phtalic acid derivatesdisclosed in British Patent No. 1,425,343.

Chelating Agents

The detergent compositions herein may also optionally contain one ormore iron and/or manganese chelating agents. Such chelating agents canbe selected from the group consisting of amino carboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents andmixtures therein, all as hereinafter defined. Without intending to bebound by theory, it is believed that the benefit of these materials isdue in part to their exceptional ability to remove iron and manganeseions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorous are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates do not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethyelediaminedisuccinate ("EDDS"), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

The granular detergent compositions and automatic dishwashingcompositions herein have a pH above 8.5, preferably in the range of from9 to 11.

The present laundry granular compositions are preferably in a compactform, having a bulk density of at least 650 g/l, preferably at least 750g/l, but can also be in a conventional form, with densities in a rangeof from 200 g/l to 700 g/l.

In another embodiment of the invention, are provided AutomaticDishwashing Compositions:

Automatic dishwashing compositions typically contain, in addition topercarbonate a builder, such as described above, a source of alkalinity,such as silicate or carbonate, those ingredients amounting to up to 70%of the formulation. Optional ingredients include polymers and enzymes.

In still another embodiment of the invention, are provided LaundryAdditive Compositions:

Such compositions typically contain the bleaching agent at levels offrom 15 to 80% by weight.

Optional Ingredients

Other ingredients which are known for use in detergent compositions mayalso be used as optional ingredients in the various embodiments of thepresent invention, such as bleach activators, bleach catalysts, otherbleaching agents, polymers, enzymes, suds suppressing agents, fabricsoftening agents, in particular fabric softening clay, as well as dyes,fillers, optical brighteners, pH adjusting agents, non builderalkalinity sources, enzyme stability agents, hydrotopes, solvents,perfumes.

The Percarbonate Particles

The compositions herein contain from 1% to 40%, preferably from 3% to30% by weight, most preferably from 5% to 25% by weight of an alkalimetal percarbonate bleach; in the form of particles having a mean sizefrom 250 to 900 micrometers, preferably 500 to 700 micrometers.

When the compositions herein are laundry additives, the level ofpercarbonate is from 20% to 80% by weight.

The alkali metal percarbonate bleach is usually in the form of thesodium salt. Sodium percarbonate is an addition compound having aformula corresponding to 2Na₂ CO₃ 3H₂ O₂. to enhance storage stabilitythe percarbonate bleach can be coated with a further mixed salt of analkali metal sulphate and carbonate. Such coatings together with coatingprocesses have previously been described in GB-1,466,799, granted toInterox on Mar. 9, 1977. The weight ratio of the mixed salt coatingmaterial to percarbonate lies in the range from 1:2000 to 1:4, morepreferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19.Preferably, the mixed salt is of sodium sulphate and sodium carbonatewhich as the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3,preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to0.5.

Other suitable coating materials are sodium silicate, of SiO2:Na2O ratiofrom 1.6:1 to 2.8:1, and magnesium silicate.

Commercially available carbonate/sulphate coated percarbonate bleach mayinclude a low level of a heavy metal sequestrant such as EDTA,1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an aminophosphonate,that is incorporated during the manufacturing process.

Bleach activators

The present compositions, especially the granular laundry detergentcompositions and laundry additives described above, preferably containfrom 1% to 20% by weight of the composition, preferably from 2% to 15%by weight, most preferably from 3% to 10% by weight of a peroxyacidbleach activator, in addition to the percarbonate bleaching agentdescribed above.

Peroxyacid bleach activators (bleach precursors) as additional bleachingcomponents in accordance with the invention can be selected from a widerange of class and are preferably those containing one or more N-orO-acyl groups.

Suitable classes include anhydrides, esters, amides, and acylatedderivatives of imidazoles and oximes, and examples of useful materialswithin these classes are disclosed in GB-A-1586789. The most preferredclasses are esters such as are disclosed in GB-A-836 988, 864,798, 1 147871 and 2 143 231 and amides such as are disclosed in GB-A-855 735 and 1246 338.

Particularly preferred bleach activator compounds as additionalbleaching components in accordance with the invention are the N-,N,N'N'tetra acetylated compounds of the formula ##STR2## where x can be O oran integer between 1 and 6.

Examples include tetra acetyl methylene diamine (TAMD) in which x=1,tetra acetyl ethylene diamine (TAED) in which x=2 and Tetraacetylhexylene diamine (TAHD) in which x=6. These and analogous compounds aredescribed in GB-A-907 356. The most preferred peroxyacid bleachactivator as an additional bleaching component is TAED.

Another preferred class of peroxyacid bleach compounds are the amidesubstituted compounds of the following general formulae: ##STR3##wherein R¹ is an aryl or alkaryl group with from about 1 to about 14carbon atoms, R² is an alkylene, arylene, and alkarylene groupcontaining from about 1 to about 14 carbon atoms, and R⁵ is H or analkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L canbe essentially any leaving group. R¹ preferably contains from about 6 to12 carbon atoms. R² preferably contains from about 4 to 8 carbon atoms.R¹ may be straight chain or branched alkyl, substituted aryl oralkylaryl containing branching, substitution, or both and may be sourcedfrom either synthetic sources or natural sources including for example,tallow fat. Analogous structural variations are permissible for R². Thesubstitution can include alkyl, aryl, halogen, nitrogen, sulphur andother typical substituent groups or organic compounds. R⁵ is preferablyH or methyl. R¹ and R⁵ should not contain more than 18 carbon atomstotal. Amide substituted bleach activator compounds of this type aredescribed in EP-A-0170386.

Another class of bleach activators to use in combination withpercarbonate comprises C₈, C₉, and/or C₁₀ (6-octanamidocaproyl)oxybenzenesulfonate, 2-phenyl-(4H)3,1 benzoxazin-4-one, benzoyllactampreferably benzoylcaprolactam and nonanoyl lactam preferably nonanoylcaprolactam.

Bleaching agents

The granular laundry detergent, automatic dishwashing compositions orlaundry additives herein may contain an additional bleaching agent, inaddition to the percarbonate.

The additional bleaching agent, if used, is either an inorganic persaltsuch as perborate, persulfate, or a preformed organic peracid orperimidic acid, such as N,N phtaloylaminoperoxy caproic acid,2-carboxy-phtaloylaminoperoxy caproic acid, N,N phtaloylaminoperoxyvaleric acid, Nonyl amide of peroxy adipic acid, 1,12diperoxydodecanedoic acid, Peroxybenzoic acid and ring substitutedperoxybenzoic acid, Monoperoxyphtalic acid (magnesium salt, hexhydrate),Diperoxybrassylic acid.

Polymers

Also useful are various organic polymers, some of which also mayfunction as builders to improve detergency. Included among such polymersmay be mentioned sodium carboxy-lower alkyl celluloses, sodium loweralkyl celluloses and sodium hydroxy-lower alkyl celluloses, such assodium carboxymethyl cellulose, sodium methyl cellulose and sodiumhydroxypropyl cellulose, polyvinyl alcohols (which often also includesome polyvinyl acetate), polyacrylamides, polyacrylates and variouscopolymers, such as those of maleic and acrylic acids. Molecular weightsfor such polymers vary widely but most are within the range of 2,000 to100,000. Also useful are terpolymers of maleic/acrylic acid and vinylalcohol having a molecular weight ranging from 3.000 to 70.000.

Polymeric polycarboxylate builders are set forth in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. Such materials include thewater-soluble salts of homo-and copolymers of aliphatic carboxylic acidssuch as maleic acid, itaconic acid, mesaconic acid, fumaric acid,aconitic acid, citraconic acid and methylenemalonic acid.

Polyaspartate and polyglutamate dispersing agents may be used,especially with zeolite builders. Dispersing agents such aspolyasparatate preferably have a molecular weight of about 10,000.

Other useful polymers include species known as soil release polymers,such as described in EPA 185 427 and EPA 311 342.

Still other polymers suitable for use herein include dye transferinhibition polymers such as polyvinylpyrrolidone, polyvinylpyrridine,N-oxide, N-vinylpyrrolidone, N-imidazole, polyvinyloxozolidone orpolyvinylimidazole.

Enzymes

Enzymatic materials can be incorporated into the detergent compositionsherein. Suitable are proteases, lipases, cellulases, peroxidases,amylases and mixtures thereof.

A suitable lipase enzyme is manufactured and sold by Novo Industries A/S(Denmark) under the trade name Lipolase and mentioned along with othersuitable lipases in EP-A-0258068 (Novo Nordisk).

Suitable cellulases are described in e.g. WO-91117243 and WO 91/17244(Novo Nordisk).

Preferred commercially available protease enzymes include those soldunder the trade names Alcalase and Savinase by Novo Industries A/S(Denmark) and Maxatase by International Bio-Synthetics, Inc. (TheNetherlands).

Other proteases include Protease A (see European Patent Application 130756, published Jan. 9, 1985) and Protease B (see European PatentApplication Serial No. 87303761.8, filed Apr. 28, 1987, and EuropeanPatent Application 130 756, Bott et al, published Jan. 9, 1985).

Peroxidase enzymes are used in combination with oxygen sources, e.g.percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching", i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo- peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813 and in WO 91/05839.

Amylases include, for example, -bacterial amylases obtained from aspecial strain of B. licheniforms, described in more detail inGB-1,296,839 (Novo). Preferred commercially available amylases includefor example, Rapidase, sold by International Bio-Synthetics Inc. andTermamyl, sold by Novo Nordisk A/S. Fungal amylases such as Fungamyl®amylase, sold by Novo Nordisk, can also be used.

Preferred process for making the laundry detergent composition herein.

In a preferred process for making the laundry detergent compositions ofthe present invention, in particular when a high bulk density isdesired, part or all of the surfactant contained in the finishedcomposition is incorporated in the form of separate particles; saidparticles may take the form of flakes, prills, marumes, noodles,ribbons, but preferably take the form of granules. The most preferredway to process the particles is by agglomerating powders (such as e.g.aluminosilicate, carbonate) with high active surfactant pastes and tocontrol the particle size of the resultant agglomerates within specifiedlimits. Such a process involves mixing an effective amount of powderwith a high active surfactant paste in one or more agglomerators such asa pan agglomerator, a Z-blade mixer or more preferably an in-line mixersuch as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211AS, Lelystad, Netherlands, and Gebrueder Lodige Maschinenbau GmbH,D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Mostpreferably a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active surfactant paste comprising from 50% by weight to 95% byweight, preferably 70% by weight to 85% by weight of surfactant is used.The surfactant system may comprise any of the groups of anionic,nonionic, cationic, amphoteric, and zwitterionic surfactants, ormixtures of these. The paste may be pumped into the agglomerator at atemperature high enough to maintain a pumpable viscosity, but low enoughto avoid degradation of the anionic surfactants used. An operatingtemperature of the paste of 50° C. to 80° C. is typical.

A particularly suitable process of making surfactant particles from highactive surfactant pastes is more fully described in EP 510 746,published on Oct. 28, 1992.

The free-flowing surfactant particles made by the process describedabove are then mixed with other detergent components, such as theparticles containing the alkalimetal percarbonate in order to produce afinished detergent composition.

This mixing may take place in any suitable piece of equipment. Liquiddetergents such as nonionic surfactant and perfume may be sprayed on tothe surface of one or more of the constituent granules, or onto thefinished composition.

Shipping Unit

Several of these flexible pouches are preferably grouped together in ashipping unit. Preferably, the shipping unit is formed to a rectangularshape. In this manner, the shipping unit is suitable to be stacked withother similar shipping units for storage and transport. A completeassembly or pallet stack is obtained by stacking several of theseshipping units. Preferably, the shipping unit may be formed by packingseveral flexible pouches in a secondary package. The primary package ishereinafter understood to be the flexible pouch itself containing thedetergent.

The secondary package according to the present invention is flexible andnon-resistant to compression. The secondary package may be preferablymade of a wrap-around film. Preferably, the wrap-around film may be madeof polyethylene or paper based films. A paper based film is preferably afilm made out of a layer of a plastic film laminated to a layer ofpaper. More preferably, the polyethylene films have a thickness in therange of about 20 μm to 200 μm, more preferably in the range of about 50μm to 100 μm. The paper based films have preferably a weight in therange of about 50 g/m² to 200 g/m². For example, a paper based film ismade of a layer of polyethylene having a thickness of 50 μm and a layermade of paper having a weight of 80 g/m².

Preferably, the packaging process of the pouches filled with detergentinto the secondary package is achieved with a conventional verticalpacking machine, so called Vertical Form Fill Seal (=VFFS). A partialperspective view of such a vertical packing machine is shown in FIG. 1.These vertical packaging machines include inter alia at least a formingshoulder (10). The method for making the secondary package with the VFFSis a continuous batch-process. The film (1) is fed into the VFFS machinein a flat configuration. This film is carried to the forming shoulder(10) which is also the filling head (11). The film is pulled around theforming shoulder (10) which extends in a vertical tube.

By pulling the plastic film around the forming shoulder, the plasticfilm is formed into a tubular configuration with overlapping verticaledges (2). "Vertical" in the sense that these edges are parallel to thefilling direction of the VFFS machine. To maintain the tubularconfiguration of the plastic film, the overlapping vertical edges (2) ofthe film are completely or partially sealed together. Preferably, thevertical edges are only partially sealed together, i.e. the seal isinterrupted at least in one region along the vertical edges (2). Theinterruption in the seal gives a free access to the interior of thesecondary package. The dimension of this interrupted seal is such toenable a user to insert at least a finger into the interrupted region,but not great enough to allow the exit of filled primary packages (15).Preferably, the dimension of the interrupted region is such to enablethe insertion of a hand. By allowing the user to insert at least afinger or a hand into the interrupted region facilitates the opening ofthe secondary package by tearing the partial seal along the verticaledges (2). Preferably, more than one interrupted region is achieved withthe partial seal along the vertical edges (2). For example, if thevertical edge (2) is 80 cm long, a 2 cm long seal is interrupted for 11cm before the next 2 cm seal. This is repeated along the vertical edgeup to 80 cm. The same can be made to a vertical edge (2) being 50 cmlong.

The film in tubular form is further sealed on the opposite end to thefilling head so as to form a bottom seal (3) with the cross seal locatedwithin the outer clamps (14). The bag formed in this way is a secondarypackage (20) according to the present invention having an open endtowards the filling head of the forming shoulder. This secondary packagecan now be filled with several filled primary packages through thefilling head and the open end.

The filled primary packages (15) are dropped through the filling head(11) into the secondary package (20) through the open end of thesecondary package. The filled primary packages pile up from the bottomseal (3) of the secondary package. Preferably, the filled primarypackages are dropped into the secondary package in such a manner thatthe filled primary packages do not turn in the secondary package duringfalling within this secondary pouch. This is especially important whenthe shape of the filled primary packages allows a minimum packing spacein a specific direction, and not in a different direction which mayoblige the secondary package to need an increased packing space. Indeed,for rectangular filled primary packages, for example, the length of thesecondary package can be reduced by lining the filled primary packagesalong the width and not the length or the height of the primary packages. This is achieved preferably by tailoring the dimension of thesecondary package with the dimensions of the filled primary packages. Asan example, the secondary package has a rectangular shape and thefollowing dimensions: length about 38 cm, width about 14.5 cm and heightabout 14.5 cm. Consequently, four flexible pouches having the dimensionsof about 9.2 cm length, 14.5 cm width and 14.0 cm height can be packedinto this secondary package described before.

Preferably, the filled primary packages which should enter into onesecondary package are first collated together. The collating of thefilled primary packages together is achieved also without using anyfastening means, such as tape-wrapping for example. Therefore, thefilled primary packages collated together are dropped as a wholecollated bundle into the secondary package. It has been found that thiscollating of the filled primary packages further ensures that the filledpouches do not turn upside down or in any other direction during thefalling into the secondary package.

Preferably, outer clamps (14) of the VFFS hold the secondary packagearound the bottom seal during the filling of the secondary package. Theouter clamps are usually used to clamp the film while sealing and/orcutting the film. Indeed, the film is usually fixed between the twohalves of outer clamps before the sealing and/or cutting. In this casethe film around the bottom seal is first fixed between the two halves ofthe outer clamp during the filling with the filled primary packages tosupport the landing of the filled primary packages in the secondarypackage. This is to avoid that the film of the secondary package isstretched up to rupture during the landing and piling up of the filledprimary packages. It has been found that the total weight which can bedropped in this manner through the filling head into the secondarypackage without any danger for the outer clamps is up to 25 kg. However,the VFFS may be provided with an additional supporting means to supportthe landing of the filled primary packages which may carry a higherload.

Preferably, once the secondary package is filled with several filledprimary packages and the bottom seal (3) is sufficiently cooled down,the outer clamps (14) are opened and the secondary package with thefilled primary packages is advanced up to a holding means (16). Theholding means preferably holds the secondary package filled with theprimary packages during the advance of the secondary package until allfilled primary packages contained in the secondary package are under thecross seal. This holding system is preferably located below the outerclamps (14) and is made of a plane movable preferably in a directionparallel to the filling of the secondary package with the primarypackages. The filled secondary package being held by the holding meansreduces the tension on the film of the secondary package which reducesthe possibility of rupture of this film. The holding means further helpto adjust the height of the top seal on the secondary package withrespect to the height of the filled primary packages inside thesecondary package. Consequently, the holding means ensures that the topseal tightly closes the top end of the secondary package around thefilled pouches. Preferably, the holding system is further able to raiseup the secondary package filled with the primary packages towards thecross seal to correct the position of the top seal on the secondarypackage.

Consequently, the filled primary packages inside the secondary packageare preferably wrapped in a substantially tight manner such that theprimary packages have less space to turn around or upside down insidethe secondary package. This means that the secondary package filled withthe filled primary packages forms preferably a compact bundle.Nevertheless, the secondary package itself does not exert any tensionforce on the contained filled packages. Therefore, the secondary packageprevents that the filled primary packages, especially when they arefilled flexible pouches, are deformed by the secondary package. Indeed,rectangular flexible filled pouches may be deformed into a round shapewhen the filled pouches are bundled together in a stretch film wrapping,for example. The round shape of the filled flexible pouches isdisadvantageous when stacking bundles of filled flexible pouches oneover another, since the stability of the stacking is lower with respectto stacked rectangular pouches.

As another preferred option, before sealing the top end opposed to thebottom seal of the secondary package, the outer clamps are preferablysubstantially closed again and the film advance system of the film inthe VFFS is reversed. In this manner the secondary package is pulled upagain until the filled primary packages are at least partially pressedagainst the outer clamps. Indeed, the outer clamps are substantiallyclosed such that the filled primary packages cannot pass through theouter clamps. Preferably, the outer clamps are closed more than 50%,more preferably at about 80%. This reduces the length of the film usedfor a secondary package. Consequently, the filled primary packagesinside the secondary package are preferably wrapped in a substantiallytight manner such that the primary packages have less space to turnaround or upside down inside the secondary package. This means that thesecondary package filled with the filled primary packages preferablyforms a compact bundle. It has been found that the wrapping of thefilled primary package with the secondary package is further improved,if this reversing of the film advance system in the VFFS is combinedwith the holding system, as described before. Furthermore, the filledsecondary package being held by the holding means reduces the tension onthe film of the secondary package which reduces the possibility ofrupture of this film.

To make a top seal (4) the outer clamps are fully closed. Once theclamps are fully closed, a top seal (4) is made opposite to the bottomseal closing completely the secondary package with the filled primarypackages. Furthermore, this closed secondary package is cut above thetop seal. Once the top seal is cooled down, the closed and finishedsecondary package is released from the outer clamps. This packing systemdescribed above preferably uses a sufficiently tight film wrapping formaking a bundle of primary packages without deforming the primarypackages. Indeed, the filled primary packages are not under substantialtension within the secondary package according to the present inventioncompared to a stretch film, for example. Nonetheless, the primarypackages are sufficiently tightly bundled such that the primary packagesare prevented from substantial movement inside the secondary package.

Preferably, the bottom seal (3) and/or the top seal (4) are interruptedseals and not continuous seals. Usually, the overlapping vertical edges(2) along the bottom seal and the top seal are completely sealed to thebottom and top seal. However, this does not allow the exit of a filledprimary package located in an extremity of the secondary package nearthe bottom or top seal. Indeed, only around the middle of the secondarypackage, the opening of the overlapping vertical edges is wide enough toallow filled primary packages to exit the secondary package. A filledprimary package being in an extremity can only exit the secondarypackage, if the filled primary packages located in the middle portion ofthe secondary package are first extracted from the inside of thesecondary package. Consequently, only when the filled primary packageslocated in an extremity can be brought to about the middle portion ofthe secondary package, can these filled primary packages extracted outfrom the secondary package.

On the contrary, it has been found that if the overlapping verticaledges (2) are not sealed at all or only partially sealed to the bottomand/or top seal of the secondary package at least at the region (2a) ofoverlap of the vertical edges along the bottom and/or top seal, all thefilled primary packages can be extracted out from the secondary packagein an easier manner and often without the whole procedure as describedbefore. Indeed, the non-sealed or partially sealed part of theoverlapping vertical edges allows a sufficient widening of the openingbetween the vertical edges also near the bottom and/or top seal.Consequently, a filled primary package at the extremity of a secondarypackage can be directly extracted out from the secondary package in aneasier manner and often without emptying first the secondary package.

To achieve that the overlapping vertical edges (2) are not sealed oronly partially sealed to the bottom (3) and/or the top seal (4), thecross seal comprises an interruption in the sealing area correspondingto the whole or part of the overlapping vertical edges. Thisinterruption in the sealing area avoids that the overlapping verticaledges are completely sealed together with the bottom and/or the top sealof the secondary package. The partial seal of the overlapping verticaledges to the bottom and/or top seal further prevents that theoverlapping vertical edges are loose and flap around. Indeed, loose orflapping overlapping vertical edges may of hindrance for the handling ofthe secondary package.

Packing the primary packages according to the present invention asdescribed before further allows to reduce the costs of the packagingnecessary for handling, storing and transportation of the filled primarypackages. Furthermore, the packing of the primary packages into thesecondary packages according to the present invention is relatively easymanner which also reduces the manufacturing costs.

Preferably, the closed and finished secondary package falls onto a feedsection which brings the closed secondary package containing the filledpouches to a location where the secondary packages can be stacked oneover another to form a pallet. It has been found that the granular orpowdered detergent according to the present invention contained in thepouches and stacked one over another within the secondary package asdescribed before does not substantially cake such that the detergent isnot sticked or aggregated into one insoluble block. Preferably, tiesheets are placed between the stacked shipping units. The tie sheetsincrease the friction between the stacked shipping units. Consequently,the tie sheets substantially impede any slipping of the shipping unitswhen stacked one over another increasing the stability of the pallet.

Another possibility to substantially impede any slipping of the shippingunits when stacked one over another is to apply a glue or an adhesive topart of the outermost surface of the secondary package or to make thesecondary package out of an embossed film. The glue or adhesive can besprayed onto at least part of the outermost surface of the secondarypackage. The embossed film is preferably made of anti-slip dimplesembossed at least on certain areas of the film of the secondary packagebefore the film is carried to the forming shoulder of the VFFS machine.For a further improved stability of the pallet the embossed film can becombined with the tie sheets described before. Additionally, the wholepallet may be further stabilized, especially for transportation, with astretch film, for example, wrapped around the pallet.

The pallet made as described before allows to eliminate any furtherouter cases which carry the compression force from the stacked assembly.This results in a substantial cost saving in the total amount ofpackaging material used for making pallets suitable for storage andtransportation. Furthermore, waste is also substantially reduced.Indeed, the outer cases are usually not re-used, but simply disposed. Ithas been found that the pallet according to the present invention canreduce the waste by at least 50%, preferably at least 80% when comparedto pallets using corrugated cardboard as outer cases.

EXAMPLE

The following granular laundry detergent composition was prepared:

    ______________________________________                                                              % by weight                                             ______________________________________                                        Anionic surfactant agglomerate*                                                                       30                                                      Layered silicate compacted granule 18                                         (supplied by Hoechst under trade name SKS-6)                                  Percarbonate** 25                                                             TAED agglomerate 9                                                            Suds suppressor agglomerate 2                                                 Perfume encapsulate 0.2                                                       Granular dense soda ash 8.4                                                   Granular acrylic-maleic copolymer 3.2                                         Enzymes 3.6                                                                   Granular soil release polymer 0.6                                              100                                                                        ______________________________________                                         *Anionic surfactant agglomerates were made from a 78% active surfactant       paste which comprises C45AS/C35AE3S (alkyl sulfate/alkyl ethoxy sulfate)      in the ratio of 80:20. The paste was agglomerates with a powder mixture       according to the process described in EPA 510 746. The resulting anionic      surfactant granule had a composition of 30% C45AS, 7.5% C35AE3S, 24%          zeolite, 20% carbonate, 2.5% CMC, 12% acrylicmaleic copolymer, and the        balance of moisture.                                                          **Percarbonate coated with 2.5% carbonate/sulphate with mean particle siz     of 500 microns.                                                          

The mixture of granular ingredients listed above was placed inside a 140liter rotating drum that operates at 25 rpm. While operating the drum amixture of nonionic surfactant (C25E3) and a 20% aqueous solution ofoptical brightener at ratios of 14:1 were sprayed onto the granularmixture to a level of 7% by weight of the granular components. Thespraying time was about 1-2 minutes. Immediately afterwards, perfume wassprayed on, at a level of 0.5% by weight of the granular components,while rotating the drum. Then, without stopping the rotation of thedrum, a flow aid was slowly added to the mixer, taking about 30 seconds.The type of flow aid used in the example was partially hydrated zeoliteA (6% moisture) and the level of addition was 8%. Once the addition offlow aid was finished, the mixer was allowed to rotate for about 1minute and was then stopped. The finished product was then removed fromthe rotating drum. The finished product had a cake strength of less than50 g/cm², at about 20 g/cm².

This finished product was filled into a flexible pouch and the flexiblepouches were grouped together in a shipping unit within a secondarypackage according to the present invention. These shipping unit werethan stacked in an assembly forming a pallet. It has been found that thepallet was sufficiently stable during storing and transportation.Furthermore, it has been found that the detergent composition inside theflexible pouches did not substantially cake. This was true wherever thedetergent composition was located in the stacked assembly. It has beenfound that even the detergent composition located in the lowest positionof the stacked assembly, where the whole weight of the rest of thepallet is carried, does not substantially cake.

What is claimed is:
 1. A shipping unit comprising more than one flexiblepouch and a secondary package, each flexible pouch being filled with agranular laundry detergent, the secondary package containing the filledpouches of the shipping unit and keeping the filled pouches together inthe shipping unit, the secondary package being closed so that itprevents the exit of any of the filled pouches prior to opening of theshipping unit, wherein the secondary package is flexible andnon-resistant to compression force when the shipping unit is stackedwith other shipping units in an assembly, and the granular laundrydetergent contained in each flexible pouch has a cake strength of lessthan or equal to 200 g/cm².
 2. A shipping unit according to claim 1wherein the granular laundry detergent contained in each flexible pouchhas a cake strength of less than 100 g/cm² and the density of thegranular laundry detergent is higher than 600 g/l.
 3. A shipping unitaccording to claim 1 wherein each flexible pouch of the shipping unit issubstantially free of head space when the pouch is filled and sealed. 4.A shipping unit according to claim 1 wherein the filled pouches whichenter into one secondary package are first bundled together.
 5. Ashipping unit according to claim 1 wherein the secondary package is madeof a film wrapping applied so that the filled pouches are not undersubstantial tension within the secondary package such that the filledpouches are not substantially deformed by the secondary package.
 6. Ashipping unit according to claim 1 wherein the shipping unit weights upto 50 kg.
 7. A shipping unit according to claim 1 wherein the secondarypackage is made of an embossed film to increase the friction between thesecondary packages.
 8. An assembly of shipping units or a pallet unit inwhich the shipping units are stacked one over another and the shippingunit is according to claim
 1. 9. An assembly according to claim 8wherein tie sheets are placed in the assembly between the stackedshipping units.
 10. An assembly according to claim 8 wherein theassembly is wrapped around with a stretch film.